Compositions and methods for reducing herbicidal injury

ABSTRACT

A method and compositions for reducing injury to crops, especially wheat and sorghum, by thiolcarbamate herbicides employing compounds having in common the base structure ##STR1## wherein Y and Y&#39; are oxygen or sulfur.

This invention relates to novel compositions and methods for reducing ornullifying injury to young crop plants by selective herbicides. Morespecifically, this invention relates to novel compositions and methodsfor reducing injury to young crop plants by herbicides, such asthiolcarbamate herbicides, which comprises treating the habitat of thecrop plant or the seed of the crop plant prior to planting, with anantagonistic agent for the herbicide.

Thiolcarbamate herbicides such as triallate, diallate,S-ethyl-N,N-dipropylthiolcarbamate (also referred to as EPTC),S-ethyl-N-ethylthiolcyclohexanecarbamate (cycloate),S-propyl-N-butyl-N-ethylthiolcarbamate (pebulate),S-ethyl-N,N-diisobutylthiolcarbamate (butylate),S-propyl-N,N-dipropylthiolcarbamate (vernolate), and the like are veryuseful for controlling certain weeds in the presence of other growingplants. However, many of these herbicides injure certain crop plants,slowing growth and development at application rates necessary to stuntor kill the weeds. As a consequence, certain of these herbicides can notbe employed for controlling weeds in the presence of certain crops, someof which crops are important commodities in the world food supply.Obviously, there is a need for a method of reducing or nullifying theinjury of the crop plant by the thiolcarbamate herbicide while notaffecting the herbicidal action on the weed to be controlled.

There is provided by this invention a novel method of reducing ornullifying injury to the desired crop plant by thiolcarbamate herbicideswhich does not interfere with the herbicidal action on the weed to becontrolled. There are also provided novel compositions for treating thesoil or the crop seed to reduce or nullify injury to the crop bythiolcarbamate herbicides.

The compounds which are useful in reducing or eliminating crop injuryare sometimes referred to as antagonistic agents, antidote compounds, orsafening agents. Antagonistic agents for the purpose of this inventionare defined as compounds which counteract the herbicidal action ofthiolcarbamate herbicides, thereby reducing or nullifying injury to thecrop plant, the crop or crop seed by the herbicide but which exhibitlittle or no toxicity to the crop plant, the crop or crop seed atsafening effective rates of application. Although the mechanism by whichthese compounds reduce the herbicidal activity of the thiolcarbamateherbicide on crop plants without reducing the effective control ofundesired plants or weeds, is not fully understood, the herbicide testprogram has confirmed the phenomenon for a wide variety of compoundshaving in common the base structure ##STR2## wherein Y and Y' are oxygenor sulfur. These compounds when employed with a thiolcarbamate herbicidereduce the injury to crop plants by the thiolcarbamate herbicide,particularly the injury to wheat and sorghum. The compounds which arepreferred antagonistic agents with thiolcarbamate herbicides for theselective control of undesired plants in the presence of wheat andsorghum are described by the formula ##STR3## wherein Y and Y' are eachindependently oxygen or sulfur and, when Y and Y' are both sulfur, R isalkyl, alkenyl, alkynyl, haloalkenyl, substituted alkyl or phenyl, R¹ ishydrogen, alkyl, haloalkenyl or alkenyl and R² is alkyl, phenylsubstituted alkyl, phenyl or substituted phenyl, or R¹ and R² when takentogether are alkylene of the empirical formula --C_(n) H_(2n) -- whereinn is an integer of from 4 through 8, inclusive, having from 4 through 8carbons in a continuous chain between the nitrogen terminal bonds or agroup of the formula wherein each R³ is independently hydrogen, halo orlower alkyl; when one of Y and Y' is oxygen, R is alkyl, substitutedalkyl, phenyl, substituted phenyl, alkenyl or haloalkenyl, R¹ ishydrogen, alkyl or substituted alkyl and R² is alkyl, phenyl orsubstituted phenyl, lower alkoxybenzyl or R¹ and R² when taken togetherare alkylene of the empirical formula --C_(n) H_(2n) wherein n is aninteger of from 4 through 8, inclusive, having from 4 through 8 carbonsin a continuous chain between the nitrogen terminal bonds or a group ofthe formula ##STR4## wherein each R³ is indendently hydrogen, halo orlower alkyl; and when both Y and Y' are oxygen, R is alkyl or phenyl, R¹is alkyl, phenyl or substituted phenyl and R² is hydrogen, alkyl,alkenyl or haloalkenyl or R and R¹ when taken together are alkylene ofthe empirical formula --C_(n) H_(2n) wherein n is an integer of from 4through 8, inclusive, having from 4 through 8 carbons in a continuouschain between the nitrogen terminal bonds or a group of the formula##STR5## wherein each R³ is independently hydrogen, halo or lower alkyl.

The amount of such antagonistic agents employed in methods andcompositions of this invention will very according to the particularthiolcarbamate herbicide with which the agent is employed and the rateof application of the herbicide. In each instance the amount ofantagonistic agent employed is a safening effective amount. By asafening effective amount is meant an amount which reduces crop injuryby the thiolcarbamate herbicide. In the tests employed in illustratingthis invention, the amount of crop injury was reduced by at least 15percent. In certain instances, a significant level of reduction of cropinjury may be as low as about 10 percent and in other instances no lowerthan 20 percent. The reduction in level of crop injury is defined as thedifference between the observed percentage of crop injury by thethiolcarbamate herbicide without the safening agent and the observedpercentage lf crop injury by the thiolcarbamate herbicide employed inconjunction with a safening effective amount of an antagonistic agent asdefined herein.

Preferred alkyl are aliphatic hydrocarbons having from 1 through 18,inclusive, carbons. The configuration of the structure can bestraight-chain, branched-chain, cyclic or a mixed configuration havingboth branched and cyclic moieties. More preferred alkyl have from 1through 6, inclusive, carbons.

As employed herein, the terms "lower alkyl" and "lower alkoxy" designatethose groups wherein the aliphatic chain is straight or branched and hasfrom 1 through 4 carbons, inclusive.

As employed herein, the term "substituted phenyl" designates phenylgroups of the formula ##STR6## wherein each Z is independently halo,trihalomethyl, hydroxyl, nitro, lower alkyl or lower alkoxy, and x is aninteger from 1 through 3, inclusive, provided that no more than two Z'sare nitro and that no more than one Z is hydroxyl. The term "halo"designates a halogen atom selected from fluorine, chlorine, bromine andiodine. Preferred halo are chloro and bromo. Preferred trihalomethyl istrifluoromethyl.

Preferred alkenyl have from 2 through 8, inclusive, carbons. Morepreferred alkenyl have from 3 through 6, inclusive, carbons. Still morepreferred alkenyl have 3 carbons and have the unsaturated bond in the2-position.

Preferred haloalkenyl have from 2 through 8, inclusive, carbons and 1through 3, inclusive, halogens. More preferred haloalkenyl have from 3through 6, inclusive, carbons and 1 through 3, inclusive, halogens.Still more preferred haloalkenyl have from 3 through 6, inclusive,carbons and 1 through 3, inclusive, chlorines.

Preferred haloalkynyl have from 2 through 8, inclusive, carbons and 1through 3, inclusive, halogens. More preferred haloalkynyl have from 3through 6, inclusive, carbons and 1 through 3, inclusive, halogens.Still more preferred haloalkynyl have from 3 through 6, inclusive,carbons and 1 through 3, inclusive, chlorines.

Preferred substituted alkyl have from 1 through 3, inclusive,substituents selected from the group consisting of acetyl, acetyloxy,lower alkylthio, amino, carbamoyl, dilower alkylcarbamoyl, cyano,hydroxyl, phenyl, substituted phenyl, phenoxyl and substituted phenoxyl,the substituents of which are the same as the substituents ofsubstituted phenyl. More preferred substituted alkyl have, in thealiphatic portion of the group, from 1 through 6, inclusive, carbons.Still more preferred substituted alkyl have one substituent selectedfrom the aforementioned group.

The compounds employed herein as antagonistic agents are either knowncompounds or are readily prepared from known compounds by old methodsknown to the skilled chemist.

Thiolcarbamate herbicides are widely known in the art. U.S. Pat. Nos.3,330,643, 2,913,327, 3,175,897, 3,185,720 and 3,198,786 are but a fewof the many patents disclosing thiolcarbamate herbicides which havepublished in the United States and other countries. Particularlyeffective safening properties are obtained with selectivethiolcarbamates of the formula ##STR7## where R' is an organic aminosubstituent having the nitrogen atom connected directly to the carbon ofthe ##STR8## and to two other carbon atoms and where R" represents anon-aromatic unsaturated radical. By non-aromatic is meant that a carbonatom which is part of an aromatic ring is not connected directly to thesulfur. The valences of the amino substituent represented by R' arepreferably satisfied by lower alkyl groups but if the chain isinterrupted by oxygen or sulfur, compounds having higher molecularweights maintain high biological activity. Moreover, heterocyclic aminosubstituents are especially efficacious. The unsaturated grouprepresented by R" is preferably an alkenyl group either unsubstituted orsubstituted by halogen although the presence of halogen servessignificantly to support the biological activity. Typical examples of R"comprise cis- and trans-2,3-dichloro-2-butenyl, 3-chloro-2-butenyl,2-chloroallyl, 2-bromoallyl, 3-chloroallyl, cis- andtrans-2,3-dichloroallyl, 3-iodoallyl, 3-iodo-2-butenyl,2,3-diodo-2-butenyl, 2-fluoro-3-chloroallyl, vinyl, allyl, 2-butenyl,4-chloro-2-butenyl, 2-iodoallyl, 3-bromoallyl, and 2,3-dibromoallyl.

Particularly good safening of diallate, triallate, vernolate, pebulate,butylate, cycloate, molinate and EPTC herbicides with regard to wheatand sorghum, especially wheat, has been found employing the safeningmethods and compositions of the present invention.

The method and compositions of this invention are illustrated by thefollowing examples.

EXAMPLES 1 THROUGH 169

The safening effectiveness of representative antagonistic agents onrepresentative thiolcarbamate herbicides with respect to wheat andsorghum is shown by the test results presented in Table I. For eachantagonistic agent, there is shown the percent inhibition of the plantsby the thiolcarbamate herbicide and the antagonistic agent and thesafening effect of the antagonistic agent in terms of reduction ofpercent inhibition which is determined by subtracting the percentinhibition of the thiolcarbamate herbicide in a specified amount and theantagonistic agent in a specified amount from the percent inhibition ofthe thiolcarbamate herbicide in the same specified amount but with noantagonistic agent. These results are obtained by the followingprocedure:

A good grade of top soil is placed in an aluminum pan and compacted to adepth of 3/8 to 1/2 inch from the top of the pan. A predetermined numberof seeds of each of the plant species to be tested are placed on top ofthe soil in the pans. A quantity of soil sufficient to substantiallyfill the pan is measured and placed in a suitable container. A measuredquantity of the antagonistic agent dispersed or dissolved in a suitablecarrier is sprayed on the soil in the container. A measured quantity ofthe thiolcarbamate herbicide dispersed or dissolved in a suitablecarrier is then sprayed on the soil in the container already treatedwith the safening agent.

The quantity of thiolcarbamate herbicide and antagonistic agent isexpressed in terms of kilograms per hectare for ease of comparing thegreenhouse test results with field results. The soil containing theantagonistic agent and/or thiolcarbamate herbicide is thoroughly mixed.This mixing is sometimes referred to as incorporation of the herbicideand antagonistic agent into the soil. The mixing or incorporationprovides a substantially uniform distribution of the antagonistic agentand herbicide throughout the soil. The seeds are covered with the soilcontaining the antagonistic agent and thiolcarbamate herbicide and thepans are leveled. The pans are then placed on a sand bench in thegreenhouse and watered from below as needed. The plants are observed atthe end of approximately 21 days and the results in terms of percentinhibition of each seed lot are recorded. For each test series a pan ofplants is also prepared containing no thiolcarbamate herbicide and noantagonistic agent as a control. Additionally, for each test, a pan ofplants is prepared with soil covering the seed containing nothiolcarbamate herbicide and only the measured amount of antagonisticagent being incorporated into the soil covering the seeds to ascertainany herbicidal effect of the antagonistic agent alone. For each seriesof tests the herbicidal effect of the thiolcarbamate herbicide isobserved from pans of plants treated with the same quantity of herbicidealone.

In the tables herein, the columns headed Percent Inhibition contain theobservations of test pans of plants which quantify the response ofplants to a combination treatment of thiolcarbamate herbicide andsafening agent. Likewise, the columns headed Safening Effect (%) containthe difference between the response of plants to treatment withthiolcarbamate herbicide and the response of plants to a combinationtreatment of the same thiolcarbamate herbicide and safening agent.

                                      TABLE I                                     __________________________________________________________________________           Amount of triallate       Amount    Percent                                                                             Safening                     Example No.                                                                          Herbicide (kg./ha.)                                                                     Antagonistic Agent                                                                            (kg./ha.)                                                                          Crop Inhibition                                                                          Effect(%)                    __________________________________________________________________________    1      0.28      Allylthionocarbanilate                                                                        4.48 Sorghum                                                                            40    55                                  1.12      Allylthionocarbanilate                                                                        4.48 Sorghum                                                                            50    49                                  4.48      Allylthionocarbanilate                                                                        4.48 Sorghum                                                                            60    38                           2      0.28      Isopropyl-N-butylcar-                                                                         4.48 Sorghum                                                                            35    60                                            banilate                                                            1.12      Isopropyl-N-butylcar-                                                                         4.48 Sorghum                                                                            70    29                                            banilate                                                     3      0.28      Allyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            20    75                                            carbanilate                                                         1.12      Allyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            30    69                                            carbanilate                                                         4.48      Allyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            65    33                                            carbanilate                                                  4      0.28      Methyl-N-ethyldithio-                                                                         4.48 Wheat                                                                              10    50                                            carbanilate                                                         0.28      Methyl-N-ethyldithio-                                                                         4.48 Sorghum                                                                            60    35                                            carbanilate                                                  5      0.14      2-chloroallyl-para-                                                                           4.48 Sorghum                                                                            40    40                                            ethoxythiolcarbanilate                                       6      0.14      2-chloroallyl-para-methoxy-                                                                   4.48 Wheat                                                                              50    20                                            thiolcarbanilate                                             7      0.14      2-chloroallyl-N-3-chloro-                                                                     4.48 Wheat                                                                              45    25                                            2-butenyldithiocarbanilate                                          0.14      2-chloroallyl-N-3-chloro-                                                                     4.48 Sorghum                                                                            50    30                                            2-butenyldithiocarbanilate                                   8      0.14      Butyl-3,4-dichlorodithio-                                                                     4.48 Wheat                                                                              40    30                                            carbanilate                                                         0.14      Butyl-3,4-dichlorodithio-                                                                     4.48 Sorghum                                                                            45    35                                            carbanilate                                                  9      0.14      Tert.butylthiolcarbanilate                                                                    4.48 Wheat                                                                              25    55                                  0.14      Tert.butylthiolcarbanilate                                                                    4.48 Sorghum                                                                            45    25                                  0.56      Tert.butylthiolcarbanilate                                                                    4.48 Wheat                                                                              70    27                                  0.56      Tert.butylthiolcarbanilate                                                                    4.48 Sorghum                                                                            60    34                           10     0.14      Ethyl-meta-methylthiol-                                                                       4.48 Wheat                                                                              20    60                                            carbanilate                                                         0.14      Ethyl-meta-methylthiol-                                                                       4.48 Sorghum                                                                            40    30                                            carbanilate                                                  11     0.14      Methyl-meta-methylthiol-                                                                      4.48 Wheat                                                                              20    50                                            carbanilate                                                  12     0.14      Allyl-N-methyldithio-                                                                         4.48 Wheat                                                                              35    25                                            carbanilate                                                         0.14      Allyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            20    75                                            carbanilate                                                         0.56      Allyl-N-methyldithio-                                                                         4.48 Wheat                                                                              80    20                                            carbanilate                                                         0.56      Allyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            45    53                                            carbanilate                                                  13     0.14      Methyl-N-ethyldithio-                                                                         4.48 Wheat                                                                              20    40                                            carbanilate                                                         0.14      Methyl-N-ethyldithio-                                                                         4.48 Sorghum                                                                            45    50                                            carbanilate                                                         0.56      Methyl-N-ethyldithio-                                                                         4.48 Wheat                                                                              80    20                                            carbanilate                                                         0.56      Methyl-N-ethyldithio-                                                                         4.48 Sorghum                                                                            65    33                                            carbanilate                                                  14     0.14      Propyl-N-methylthiol-                                                                         4.48 Wheat                                                                              0     70                                            carbanilate                                                         0.14      Propyl-N-methylthiol-                                                                         4.48 Sorghum                                                                            65    20                                            carbanilate                                                  15     0.14      Propyl-N-methylthiol-                                                                         4.48 Wheat                                                                              35    35                                            carbanilate                                                         0.14      Propyl-N-methylthiol-                                                                         4.48 Sorghum                                                                            45    40                                            carbanilate                                                  16     0.14      Butyl-N-methylthiol-                                                                          4.48 Wheat                                                                              0     70                                            carbanilate                                                         0.14      Butyl-N-methylthiol-                                                                          4.48 Sorghum                                                                            40    45                                            carbanilate                                                         0.56      Butyl-N-methylthiol-                                                                          4.48 Sorghum                                                                            60    38                                            carbanilate                                                  17     0.14      Isobutyl-N-methyl-                                                                            4.48 Wheat                                                                              40    30                                            carbanilate                                                         0.14      Isobutyl-N-methyl-                                                                            4.48 Sorghum                                                                            15    70                                            carbanilate                                                  18     0.14      Propyl-N-butylthiol-                                                                          4.48 Wheat                                                                              45    25                                            carbanilate                                                  19     0.14      2-methylallyl-N-methyl-                                                                       4.48 Wheat                                                                              0     70                                            dithiocarbanilate                                                   0.14      2-methylallyl-N-methyl-                                                                       4.48 Sorghum                                                                            25    60                                            dithiocarbanilate                                                   0.56      2-methylallyl-N-methyl-                                                                       4.48 Sorghum                                                                            55    43                                            dithiocarbanilate                                            20     0.14      3-chloroallyl-N-ethyl-                                                                        4.48 Sorghum                                                                            40    45                                            dithiocarbanilate                                                   0.56      3-chloroallyl-N-ethyl-                                                                        4.48 Sorghum                                                                            85    13                                            dithiocarbanilate                                            21     0.14      Allyl-N-ethyldithio-                                                                          4.48 Sorghum                                                                            50    35                                            carbanilate                                                  22     0.14      2-propynyl-N-ethyl-                                                                           4.48 Wheat                                                                              20    20                                            dithiocarbanilate                                                   0.14      2-propynyl-N-ethyl-                                                                           4.48 Sorghum                                                                            70    15                                            dithiocarbanilate                                            23     0.14      Butyl-N-ethyldithio-                                                                          4.48 Sorghum                                                                            50    35                                            carbanilate                                                         0.56      Butyl-N-ethyldithio-                                                                          4.48 Sorghum                                                                            75    23                                            carbanilate                                                  24     0.14      Sec.butyl-N-ethyl-                                                                            4.48 Sorghum                                                                            10    75                                            dithiocarbanilate                                                   0.56      Sec.butyl-N-ethyl-                                                                            4.48 Sorghum                                                                            30    68                                            dithiocarbanilate                                            25     0.14      Isobutyl-N-ethyl-                                                                             4.48 Sorghum                                                                            0     85                                            dithiocarbanilate                                                   0.56      Isobutyl-N-ethyl-                                                                             4.48 Sorghum                                                                            45    53                                            dithiocarbanilate                                            26     0.14      2-chloroallyl-N-allyl-3,4-                                                                    4.48 Sorghum                                                                            15    70                                            dichlorodithiocarbanilate                                           0.56      2-chloroallyl-N-allyl-3,4-                                                                    4.48 Sorghum                                                                            65    33                                            dichlorodithiocarbanilate                                    27     0.14      Methyl-N-allyl-3,4-                                                                           4.48 Sorghum                                                                            35    50                                            dichlorodithiocarbanilate                                           0.56      Methyl-N-allyl-3,4-                                                                           4.48 Sorghum                                                                            70    28                                            dichlorodithiocarbanilate                                    28     0.14      Isopropyl-N-ethyldithio-                                                                      4.48 Sorghum                                                                            10    75                                            carbanilate                                                         0.56      Isopropyl-N-ethyldithio-                                                                      4.48 Sorghum                                                                            75    23                                            carbanilate                                                  29     0.14      Ethyl-N-ethyldithio-                                                                          4.48 Wheat                                                                              0     40                                            carbanilate                                                  30     0.14      Allyl-N-ethyldithio-                                                                          4.48 Wheat                                                                              5     35                                            carbanilate                                                         0.56      Allyl-N-ethyldithio-                                                                          4.48 Wheat                                                                              60    28                                            carbanilate                                                  31     0.14      2-chloroallyl-para-chloro-                                                                    4.48 Wheat                                                                              25    15                                            N-ethyldithiocarbanilate                                     32     0.14      3-chloropropyl-N-ethyl-                                                                       4.48 Wheat                                                                              20    20                                            thionocarbanilate                                            33     0.14      2-chloroethyl-N-ethyl-                                                                        4.48 Wheat                                                                              25    15                                            thionocarbanilate                                            34     0.14      Phenyl-N-methyldithio-                                                                        4.48 Wheat                                                                              15    25                                            carbanilate                                                  35     0.14      3-chloroallyl-N-methyl-                                                                       4.48 Wheat                                                                              20    30                                            dithiocarbanilate                                                   0.14      3-chloroallyl-N-methyl-                                                                       4.48 Sorghum                                                                            20    35                                            dithiocarbanilate                                            36     0.14      3-chloro-2-butenyl-N-                                                                         4.48 Sorghum                                                                            30    25                                            methyldithiocarbanilate                                      37     0.14      Cyanomethyl-N-methyl-                                                                         4.48 Wheat                                                                              10    40                                            dithiocarbanilate                                                   0.14      Cyanomethyl-N-methyl-                                                                         4.48 Sorghum                                                                            40    15                                            dithiocarbanilate                                            38     0.14      Ethyl-N-methyldithio-                                                                         4.48 Wheat                                                                              25    25                                            carbanilate                                                         0.14      Ethyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            0     55                                            carbanilate                                                         0.56      Ethyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            50    40                                            carbanilate                                                  39     0.14      Propyl-N-methyldithio-                                                                        4.48 Wheat                                                                              25    25                                            carbanilate                                                         0.14      Propyl-N-methyldithio-                                                                        4.48 Sorghum                                                                            0     55                                            carbanilate                                                         0.56      Propyl-N-methyldithio-                                                                        4.48 Sorghum                                                                            30    60                                            carbanilate                                                  40     0.14      2-bromoallyl-N-methyl-                                                                        4.48 Wheat                                                                              25    25                                            dithiocarbanilate                                                   0.14      2-bromoallyl-N-methyl-                                                                        4.48 Sorghum                                                                            25    30                                            dithiocarbanilate                                            41     0.14      Carbamoylmethyl-N-methyl-                                                                     4.48 Sorghum                                                                            20    35                                            dithiocarbanilate                                            42     0.14      Methyl-N-methylthiol-                                                                         4.48 Sorghum                                                                            10    35                                            carbanilate                                                  43     0.14      Isopropyl-N-isopropyl-                                                                        4.48 Sorghum                                                                            25    20                                            thiolcarbanilate                                             44     0.14      Methyl-N-(2-cyanoethyl)-                                                                      4.48 Sorghum                                                                            25    20                                            thiolcarbanilate                                             45     0.14      Allyl-N-isopropylthiol-                                                                       4.48 Sorghum                                                                            15    30                                            carbanilate                                                  46     0.14      Ethyl-N-(2-carbamoyl-                                                                         4.48 Sorghum                                                                            0     45                                            ethyl)thiolcarbanilate                                       47     0.14      Methyl-ortho-fluorothiol-                                                                     4.48 Sorghum                                                                            25    20                                            carbanilate                                                  48     0.14      Cyclohexylthiolcarbanilate                                                                    4.48 Wheat                                                                              0     20                                  0.14      Cyclohexylthiolcarbanilate                                                                    4.48 Sorghum                                                                            20    25                                  0.56      Cyclohexylthiolcarbanilate                                                                    4.48 Sorghum                                                                            40    48                           49     0.14      Methyl-N-methyldithio-                                                                        4.48 Wheat                                                                              0     15                                            carbanilate                                                         0.14      Methyl-N-methyldithio-                                                                        4.48 Sorghum                                                                            15    55                                            carbanilate                                                  50     0.14      Ethyl-N-methyldithio-                                                                         4.48 Wheat                                                                              0     15                                            carbanilate                                                  51     0.14      Butyl-N-methyldithio-                                                                         4.48 Wheat                                                                              0     15                                            carbanilate                                                         0.14      Butyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            10    60                                            carbanilate                                                         0.56      Butyl-N-methyldithio-                                                                         4.48 Sorghum                                                                            45    53                                            carbanilate                                                  52     0.14      Methyl-N-methyl-ortho-                                                                        4.48 Sorghum                                                                            10    60                                            methyldithiocarbanilate                                             0.56      Methyl-N-methyl-ortho-                                                                        4.48 Sorghum                                                                            75    23                                            methyldithiocarbanilate                                      53     0.14      Methyl-N-methyl-para-                                                                         4.48 Wheat                                                                              0     15                                            methyldithiocarbanilate                                             0.14      Methyl-N-methyl-para-                                                                         4.48 Sorghum                                                                            10    60                                            methyldithiocarbanilate                                             0.56      Methyl-N-methyl-para-                                                                         4.48 Sorghum                                                                            20    78                                            methyldithiocarbanilate                                      54     0.14      Cyclohexyl-meta-methyl-                                                                       4.48 Sorghum                                                                            40    25                                            thiolcarbanilate                                             55     0.14      Methyl-2,6-diethyl-                                                                           4.48 Wheat                                                                              25    20                                            thionocarbanilate                                            56     0.14      Methyl-para-tert.butyl-                                                                       4.48 Wheat                                                                              20    25                                            thiolcarbanilate                                                    0.14      Methyl-para-tert.butyl-                                                                       4.48 Sorghum                                                                            15    50                                            thiolcarbanilate                                             57     0.14      2-chloroallyl-para-                                                                           4.48 Wheat                                                                              20    25                                            nitrodithiocarbanilate                                       58     0.14      Propyl-N-isopropyl-                                                                           4.48 Wheat                                                                              10    35                                            dithiocarbanilate                                            59     0.14      Ethyl-N-isopropyl-meta-                                                                       4.48 Sorghum                                                                            30    35                                            hydroxythiolcarbanilate                                      60     0.14      Isopropyl-meta-nitro-                                                                         4.48 Wheat                                                                              0     45                                            thionocarbanilate                                                   0.14      Isopropyl-meta-nitro-                                                                         4.48 Sorghum                                                                            25    40                                            thionocarbanilate                                            61     0.14      2-chloroallyl-para-                                                                           4.48 Wheat                                                                              25    20                                            fluorodithiocarbanilate                                      62     0.14      Benzyl octamethylene                                                                          4.48 Wheat                                                                              10    20                                            iminecarbothiolate                                           63     0.14      Meta-trifluoromethylbenzyl-                                                                   4.48 Sorghum                                                                            20    45                                            N,N-di-sec.butyldithiocarbamate                                     0.56      Meta-trifluoromethylbenzyl-                                                                   4.48 Sorghum                                                                            75    20                                            N,N-di-sec.butyldithiocarbamate                              64     0.14      3-cyanobutyl-N,N-di-sec.-                                                                     4.48 Sorghum                                                                            30    35                                            butyldithiocarbamate                                         65     0.14      Carbamoylmethyl-N,N-di-                                                                       4.48 Sorghum                                                                            20    45                                            sec.butylthiolcarbamate                                      66     0.14      Para-fluorobenzyl-N-methyl-                                                                   4.48 Wheat                                                                              35    35                                            dithiocarbanilate                                            67     0.28      Cyanomethyl-N-ethyl-                                                                          4.48 Wheat                                                                              35    35                                            dithiocarbanilate                                            68     0.28      Ethyl-N-propyldithio-                                                                         4.48 Sorghum                                                                            65    25                                            carbanilate                                                  69     0.28      Butyl-N-propyldithio-                                                                         4.48 Sorghum                                                                            70    20                                            carbanilate                                                  70     0.28      Hexyl-N-propylthiol-                                                                          4.48 Sorghum                                                                            35    55                                            carbanilate                                                  71     0.28      2-cyanoethyl-N-ethyl-                                                                         4.48 Wheat                                                                              50    20                                            dithiocarbanilate                                                   0.28      2-cyanoethyl-N-ethyl-                                                                         4.48 Sorghum                                                                            0     90                                            dithiocarbanilate                                                   0.56      2-cyanoethyl-N-ethyl-                                                                         4.48 Sorghum                                                                            10    88                                            dithiocarbanilate                                            72     0.28      Methyl-2-tert.butyl-6-                                                                        2.24 Wheat                                                                              60    25                                            methylthiolcarbanilate                                       73     0.28      Methyl-3-chloro-6-methyl-                                                                     2.24 Wheat                                                                              60    25                                            thionocarbanilate                                            74     0.28      Methyl-N-butylthiol-                                                                          2.24 Wheat                                                                              65    20                                            carbanilate                                                  75     0.28      Methyl-N-butyldithio-                                                                         2.24 Wheat                                                                              60    25                                            carbanilate                                                  76     0.28      2-cyclohexen-1-yl-                                                                            2.24 Wheat                                                                              55    15                                            methyldithiocarbamate                                        77     0.28      2-cyclohexen-1-yl-methyl-                                                                     4.48 Wheat                                                                              55    15                                            dithiocarbamate                                              78     0.28      2-cyclohexen-1-yl-(3-                                                                         4.48 Sorghum                                                                            35    20                                            ethoxypropyl)-dithio-                                                         carbamate                                                    79     0.28      2-cyclohexen-1-yl-diiso-                                                                      4.48 Sorghum                                                                            30    25                                            propylthiolcarbamate                                         80     0.28      Methyl-3,6-dihydro-1(2H)-                                                                     4.48 Sorghum                                                                            35    20                                            pyridinecarbonthiolate                                       81     0.28      Allyl-3,6-dihydro-1(2H)-                                                                      4.48 Sorghum                                                                            35    20                                            pyridinecarbothiolate                                        82     0.28      Isopropyl-piperidinethiono-                                                                   2.24 Wheat                                                                              55    15                                            carboxylate                                                  83     0.28      Butyl-3,6-dihydro-1(2H)-                                                                      1.12 Sorghum                                                                            35    20                                            pyridinecarbothiolate                                        84     0.28      Isopropyl-N-methyl-1-                                                                         4.48 Wheat                                                                              50    20                                            cyclohexene-1-carbamate                                      85     0.28      Ethyl-N-(1-cyclohexen-1-yl)-                                                                  4.48 Wheat                                                                              55    15                                            N-methylthiolcarbamate                                       86     0.28      Butyl-N-(1-cyclohexen-1-yl)-                                                                  2.24 Wheat                                                                              55    15                                            N-methylthiolcarbamate                                              0.28      Butyl-N-(1-cyclohexen-1-yl)-                                                                  2.24 Sorghum                                                                            30    25                                            N-methylthiolcarbamate                                       87     0.28      Ethyl-N-(1-cyclohexen-1-                                                                      5.60 Wheat                                                                              45    25                                            yl)-N-isopropylthiolcarbamate                                88     0.28      Butyl thiolcarbamate                                                                          4.48 Sorghum                                                                            25    30                           89     0.28      Methyl-N-isopropylthiono-                                                                     4.48 Wheat                                                                              20    38                                            carbanilate                                                         0.28      Methyl-N-isopropylthiono-                                                                     4.48 Sorghum                                                                            45    40                                            carbanilate                                                  90     0.28      Acetylmethyl-N-ethyldithio-                                                                   4.48 Wheat                                                                              35    23                                            carbanilate                                                         0.28      Acetylmethyl-N-ethyldithio-                                                                   4.48 Sorghum                                                                            55    30                                            carbanilate                                                  91     0.28      Ortho-fluorobenzyl-N-ethyl-                                                                   4.48 Wheat                                                                              35    23                                            dithiocarbanilate                                                   0.28      Ortho-fluorobenzyl-N-ethyl-                                                                   4.48 Sorghum                                                                            15    70                                            dithiocarbanilate                                            92     0.28      Propyl-N-propylcarbanilate                                                                    4.48 Wheat                                                                              25    33                                  0.28      Propyl-N-propylcarbanilate                                                                    4.48 Sorghum                                                                            40    45                           93     0.28      Butyl-N-propylcarbanilate                                                                     4.48 Wheat                                                                              20    38                                  0.28      Butyl-N-propylcarbanilate                                                                     4.48 Sorghum                                                                            0     85                           94     0.28      Phenyl-N-propylcarbanilate                                                                    4.48 Wheat                                                                              10    48                                  0.28      Phenyl-N-propylcarbanilate                                                                    4.48 Sorghum                                                                            65    20                           95     0.28      Methyl-N-methyl-para-                                                                         4.48 Wheat                                                                              30    28                                            chlorodithiocarbanilate                                             0.28      Methyl-N-methyl-para-                                                                         4.48 Sorghum                                                                            0     85                                            chlorodithiocarbanilate                                      96     0.28      Benzyldithiocarbamate                                                                         4.48 Sorghum                                                                            60    30                           97     0.28      Tert.butyldiisopropyl-                                                                        4.48 Wheat                                                                              30    25                                            dithiocarbamate                                              98     0.28      3-chloropropylmethylthiol-                                                                    4.48 Sorghum                                                                            55    35                                            carbamate                                                    99     0.28      Butyl-N-benzyl-N-methyl-                                                                      4.48 Wheat                                                                              20    35                                            dithiocarbamate                                              100    0.28      Methyl-N-benzyl-N-                                                                            4.48 Wheat                                                                              35    20                                            methyldithiocarbamate                                               0.28      Methyl-N-benzyl-N-                                                                            4.48 Sorghum                                                                            30    60                                            methyldithiocarbamate                                        101    0.28      Phenyldiethyldithio-                                                                          4.48 Wheat                                                                              45    25                                            carbamate                                                    102    0.28      2-chloroethyl-4-                                                                              4.48 Wheat                                                                              50    20                                            morpholinecarbothionate                                      103    0.28      2-chloroallyl-2,6-dimethyl-                                                                   4.48 Wheat                                                                              50    20                                            4-morpholinecarbothionate                                    104    0.28      Hexylhexahydro-1H-azepine-                                                                    4.48 Wheat                                                                              50    20                                            1-carbothiolate                                              105    0.28      Ethylthiolcyclohexane-                                                                        4.48 Wheat                                                                              45    35                                            carbamate                                                           0.28      Ethylthiolcyclohexane-                                                                        4.48 Sorghum                                                                            70    15                                            carbamate                                                    106    0.28      Methyl-N-butyldithiocyclo-                                                                    4.48 Wheat                                                                              30    50                                            hexanecarbamate                                                     0.28      Methyl-N-butyldithiocyclo-                                                                    4.48 Sorghum                                                                            35    50                                            hexanecarbamate                                              107    0.28      Methyl-N-methylthiono-                                                                        4.48 Wheat                                                                              20    60                                            cyclohexanecarbamate                                         108    0.28      Ethyl-N-methylthionocyclo-                                                                    4.48 Wheat                                                                              50    30                                            hexanecarbamate                                                     0.28      Ethyl-N-methylthionocyclo-                                                                    4.48 Sorghum                                                                            40    45                                            hexanecarbamate                                              109    0.28      Ethyl-N-ethylthionocyclo-                                                                     4.48 Wheat                                                                              50    30                                            hexanecarbamate                                                     0.28      Ethyl-N-ethylthionocyclo-                                                                     4.48 Sorghum                                                                            45    40                                            hexanecarbamate                                              110    0.28      Methyl-N-butylthiono-                                                                         4.48 Wheat                                                                              50    30                                            cyclohexanecarbamate                                         111    0.28      2-propynyl-2,5-dimethyl-                                                                      4.48 Wheat                                                                              60    20                                            pyrrolidinethiocarboxylate                                   112    0.28      2-chloroallyl-meta-methyl-                                                                    4.48 Wheat                                                                              75    15                                            dithiocarbanilate                                            113    0.28      Propyl-N-butylthiono-                                                                         4.48 Wheat                                                                              65    25                                            cyclohexanecarbamate                                         114    0.28      Methyl-N-benzyl-N-                                                                            4.48 Wheat                                                                              75    15                                            isopropyldithiocarbamate                                            0.28      Methyl-N-benzyl-N-                                                                            4.48 Sorghum                                                                            30    65                                            isopropyldithiocarbamate                                     115    0.28      Ethyl-N-benzyl-N-iso-                                                                         4.48 Sorghum                                                                            70    25                                            propyldithiocarbamate                                        116    0.28      Methyl-N-benzyl-N-iso-                                                                        4.48 Wheat                                                                              70    20                                            propylthiolcarbamate                                         117    0.28      Ethyl-octahydro-1H-azonine-                                                                   4.48 Wheat                                                                              75    15                                            thionocarboxylate                                                   0.28      Ethyl-octahydro-1H-azonine-                                                                   4.48 Sorghum                                                                            50    45                                            thionocarboxylate                                            118    0.14      Methyl-N-butylthiol-                                                                          4.48 Wheat                                                                              25    23                                            carbanilate                                                         0.28      Methyl-N-butylthiol-                                                                          4.48 Wheat                                                                              35    25                                            carbanilate                                                         0.14      Methyl-N-butylthiol-                                                                          4.48 Sorghum                                                                            45    20                                            carbanilate                                                  119    0.14      Methyl-N-butyldithio-                                                                         4.48 Wheat                                                                              10    38                                            carbanilate                                                         0.28      Methyl-N-butyldithio-                                                                         4.48 Wheat                                                                              35    25                                            carbanilate                                                         0.14      Methyl-N-butyldithio-                                                                         4.48 Sorghum                                                                            20    45                                            carbanilate                                                         0.28      Methyl-N-butyldithio-                                                                         4.48 Sorghum                                                                            60    28                                            carbanilate                                                  120    0.14      Para-fluorobenzyl-N-                                                                          4.48 Wheat                                                                              15    33                                            methyldithiocarbanilate                                             0.28      Para-fluorobenzyl-N-                                                                          4.48 Wheat                                                                              45    15                                            methyldithiocarbanilate                                      121    0.14      Cyanomethyl-N-ethyldithio-                                                                    4.48 Wheat                                                                              30    18                                            carbanilate                                                         0.28      Cyanomethyl-N-ethyldithio-                                                                    4.48 Wheat                                                                              30    30                                            carbanilate                                                  122    0.14      Methyl-N-isopropylthiono-                                                                     4.48 Wheat                                                                              15    33                                            carbanilate                                                         0.28      Methyl-N-isopropylthiono-                                                                     4.48 Wheat                                                                              25    35                                            carbanilate                                                         0.14      Methyl-N-isopropylthiono-                                                                     4.48 Sorghum                                                                            35    30                                            carbanilate                                                  123    0.14      Methyl-N-methylpara-chloro-                                                                   4.48 Sorghum                                                                            15    50                                            dithiocarbanilate                                                   0.28      Methyl-N-methylpara-chloro-                                                                   4.48 Sorghum                                                                            10    78                                            dithiocarbanilate                                                   0.56      Methyl-N-methylpara-chloro-                                                                   4.48 Sorghum                                                                            25    75                                            dithiocarbanilate                                                   1.12      Methyl-N-methylpara-chloro-                                                                   4.48 Sorghum                                                                            35    60                                            dithiocarbanilate                                            124    0.28      Ethyl-N-(alpha-methyl-                                                                        4.48 Sorghum                                                                            20    20                                            benzyl)dithiocarbamate                                       125    0.28      2,3,3-trichlorochlorallyl-                                                                    2.24 Wheat                                                                              20    35                                            N-(alpha-methylbenzyl)-                                                       dithiocarbamate                                              126    0.28      Propyl-N-(alpha-methyl-                                                                       8.96 Sorghum                                                                            15    25                                            benzyl)-dithiocarbamate                                      127    0.28      Methyl-N-(alpha-methyl-                                                                       8.96 Sorghum                                                                            25    15                                            benzyl)carbamate                                             128    0.28      Ortho-fluorobenzyl-N-                                                                         4.48 Sorghum                                                                            20    20                                            (alpha-methylbenzyl)thiol-                                                    carbamate                                                    129    0.28      2-bromoallyl-N-(alpha-                                                                        4.48 Sorghum                                                                            15    25                                            methylbenzyl)thiolcarbamate                                  130    0.28      2-chloroallyl-N-(alpha-                                                                       4.48 Wheat                                                                              30    25                                            methylbenzyl)thiolcarbamate                                         0.28      2-chloroallyl-N-(alpha-                                                                       4.48 Sorghum                                                                            10    30                                            methylbenzyl)thiolcarbamate                                  131    0.28      3-chloropropyldimethyl-                                                                       2.24 Wheat                                                                              40    35                                            dithiocarbamate                                                     0.28      3-chloropropyldimethyl-                                                                       2.24 Sorghum                                                                            40    20                                            dithiocarbamate                                              132    0.28      2,3,3-trichloroallyl-                                                                         1.12 Sorghum                                                                            30    30                                            diethyldithiocarbamate                                       133    0.28      3,3-dichloroallylthiol-                                                                       8.96 Sorghum                                                                            35    25                                            carbamate                                                    134    0.28      Tert.butyl(2-methylallyl)-                                                                    0.56 Wheat                                                                              50    20                                            2-propynylthiolcarbamate                                     135    0.28      2-(methylthio)ethyl-N-                                                                        4.48 Sorghum                                                                            20    70                                            ethyldithiocarbanilate                                       136    0.28      2,4-dichlorophenyl-N-                                                                         4.48 Sorghum                                                                            35    35                                            methylcarbanilate                                            137    0.28      Para-methoxyphenyl-N-                                                                         4.48 Wheat                                                                              50    25                                            ethylthionocarbanilate                                              0.28      Para-methoxyphenyl-N-                                                                         4.48 Sorghum                                                                            35    35                                            ethylthionocarbanilate                                       138    0.28      Para-methoxyphenyl-N-                                                                         2.24 Sorghum                                                                            50    20                                            methylthionocarbanilate                                      139    0.28      Methyl-N-ethyl-para-                                                                          4.48 Sorghum                                                                            25    28                                            chlorodithiocarbanilate                                      140    0.28      2-(methylthio)ethyl-N-                                                                        4.48 Sorghum                                                                            30    55                                            methyldithiocarbanilate                                             0.56      2-(methylthio)ethyl-N-                                                                        4.48 Sorghum                                                                            40    58                                            methyldithiocarbanilate                                      141    0.28      Ortho-fluorobenzyl-N-                                                                         4.48 Sorghum                                                                            50    35                                            methyldithiocarbanilate                                      142    0.28      Meta-fluorobenzyl-N-                                                                          4.48 Sorghum                                                                            65    20                                            methyldithiocarbanilate                                      143    0.28      Para-chlorophenoxymethyl-                                                                     4.48 Sorghum                                                                            40    45                                            N-methyldithiocarbanilate                                    144    0.28      Cyanomethyl-N-ethyl-                                                                          4.48 Sorghum                                                                            30    50                                            dithiocarbanilate                                                   0.56      Cyanomethyl-N-ethyl-                                                                          4.48 Sorghum                                                                            45    53                                            dithiocarbanilate                                            145    0.28      Meta-trifluoromethylbenzyl-                                                                   4.48 Sorghum                                                                            65    25                                            N-methyldithiocarbanilate                                    146    0.28      Methyl-N-propyldithio-                                                                        4.48 Sorghum                                                                            75    15                                            carbanilate                                                  147    0.14      Allylthionocarbanilate                                                                        4.48 Sorghum                                                                            50    25                           148    0.14      Cyanoethyl-N-methyl-                                                                          4.48 Sorghum                                                                            15    60                                            dithiocarbanilate                                            149    0.14      Butyl-N-isopropyldithio-                                                                      4.48 Sorghum                                                                            35    40                                            carbanilate                                                  150    0.14      Butyl-N-isopropyl-                                                                            4.48 Sorghum                                                                            10    65                                            carbanilate                                                         0.56      Butyl-N-isopropyl-                                                                            4.48 Sorghum                                                                            20    78                                            carbanilate                                                  151    0.14      Allylthionocarbanilate                                                                        4.48 Sorghum                                                                            10    50                                  0.56      Allylthionocarbanilate                                                                        4.48 Sorghum                                                                            65    28                           152    0.14      Butylthiolcarbanilate                                                                         4.48 Sorghum                                                                            25    35                           153    0.14      2-dimethylaminoethyl-N-                                                                       4.48 Sorghum                                                                            45    15                                            methyldithiocarbanilate                                      154    0.14      Allyl-meta-chlorodithio-                                                                      4.48 Sorghum                                                                            45    15                                            carbanilate                                                         0.56      Allyl-meta-chlorodithio-                                                                      4.48 Sorghum                                                                            80    13                                            carbanilate                                                  155    0.14      Methylthionocarbanilate                                                                       4.48 Sorghum                                                                            35    25                                  0.56      Methylthionocarbanilate                                                                       4.48 Sorghum                                                                            75    18                           156    0.14      2-chloroallyldithio-                                                                          4.48 Sorghum                                                                            25    35                                            carbanilate                                                         0.56      2-chloroallyldithio-                                                                          4.48 Sorghum                                                                            80    13                                            carbanilate                                                  157    0.14      2-chloroallyl-N-propyl-                                                                       4.48 Sorghum                                                                            35    25                                            dithiocarbanilate                                            158    0.14      Tert.butylthiocarbanilate                                                                     4.48 Wheat                                                                              10    20                                  0.14      Tert.butylthiocarbanilate                                                                     4.48 Sorghum                                                                            30    25                                  0.28      Tert.butylthiocarbanilate                                                                     4.48 Sorghum                                                                            30    50                           159    0.14      Propyl-N-methylthiol-                                                                         4.48 Sorghum                                                                            40    15                                            carbanilate                                                         0.28      Propyl-N-methylthiol-                                                                         4.48 Sorghum                                                                            65    15                                            carbanilate                                                         0.56      Propyl-N-methylthiol-                                                                         4.48 Sorghum                                                                            80    18                                            carbanilate                                                  160    0.14      Butyl-N-methylthiol-                                                                          4.48 Sorghum                                                                            25    30                                            carbanilate                                                         0.28      Butyl-N-methylthiol-                                                                          4.48 Sorghum                                                                            20    60                                            carbanilate                                                         0.56      Butyl-N-methylthiol-                                                                          4.48 Sorghum                                                                            35    63                                            carbanilate                                                  161    0.14      2-methylallyl-N-methyl-                                                                       4.48 Sorghum                                                                            20    35                                            dithiocarbanilate                                                   0.28      2-methylallyl-N-methyl-                                                                       4.48 Sorghum                                                                            40    40                                            dithiocarbanilate                                                   0.56      2-methylallyl-N-methyl-                                                                       4.48 Sorghum                                                                            60    38                                            dithiocarbanilate                                            162    0.07      Allyl-N-ethylthiono-                                                                          4.48 Wheat                                                                              0     10                                            carbanilate                                                         0.14      Allyl-N-ethylthiono-                                                                          4.48 Wheat                                                                              10    20                                            carbanilate                                                         0.28      Allyl-N-ethylthiono-                                                                          4.48 Wheat                                                                              50    25                                            carbanilate                                                  163    0.14      Phenyl-N-methyldithio-                                                                        4.48 Sorghum                                                                            35    20                                            carbanilate                                                  164    0.07      Cyanomethyl-N-methyl-                                                                         4.48 Sorghum                                                                            0     15                                            dithiocarbanilate                                                   0.14      Cyanomethyl-N-methyl-                                                                         4.48 Sorghum                                                                            15    40                                            dithiocarbanilate                                                   0.28      Cyanomethyl-N-methyl-                                                                         4.48 Sorghum                                                                            45    35                                            dithiocarbanilate                                                   0.56      Cyanomethyl-N-methyl-                                                                         4.48 Sorghum                                                                            65    33                                            dithiocarbanilate                                            165    0.14      Hexylhexahydro(1H)-                                                                           1.12 Wheat                                                                              35    35                                            azepine-1-carbothiolate                                      166    0.14      Methyl-N-butyldithio-                                                                         2.24 Wheat                                                                              25    45                                            cyclohexanecarbamate                                         167    0.14      Butyl-N-benzyl-N-methyl-                                                                      1.12 Wheat                                                                              50    20                                            dithiocarbamate                                              168    0.14      2,3,3-trichloroallyl-N-                                                                       2.24 Wheat                                                                              0     50                                            alpha-methylbenzyldithio-                                                     carbamic acid                                                       0.28      2,3,3-trichloroallyl-N-                                                                       2.24 Wheat                                                                              40    20                                            alpha-methylbenzyldithio-                                                     carbamic acid                                                169    0.14      2-chloroallyl-N-alpha-                                                                        4.48 Wheat                                                                              25    25                                            methylbenzylthiolcarbamate                                          0.14      2-chloroallyl-N-alpha-                                                                        4.48 Sorghum                                                                            25    50                                            methylbenzylthiolcarbamate                                          0.28      2-chloroallyl-N-alpha-                                                                        4.48 Sorghum                                                                            60    35                                            methylbenzylthiolcarbamate                                   __________________________________________________________________________

Although in the foregoing examples the safening agent is applied to thesoil before the thiolcarbamate herbicide, equivalent results areobtainable when the safening agent is applied in mixture with thethiolcarbamate herbicide or in sequence after the thiolcarbamateherbicide is applied. This also is observed in post-emergentapplications. The ability to be applied as mixtures and obtain safeningof thiolcarbamate herbicide with wheat and sorghum is confirmed in tankmix tests.

A key contribution of the present invention is that the safening orantagonistic agents when applied to seed reduce crop injury withoutreducing effective weed control by the thiolcarbamate herbicides.

EXAMPLES 170 to 180

The procedure of Examples 1 to 169 is repeated except that theantagonistic agent is applied as a seed treatment rather than as asequential spray before application of the herbicide. For seedtreatment, the antagonistic agent is mixed with an inert carriercomprising a finely-divided clay and a high surface area calciumsilicate in a range of weight percentages of active antagonistic agentto inert carrier. An excess of the antagonistic agent/inert carriermixture is thoroughly mixed with the crop seed to be protected. Withrespect to wheat seed, the following correlation of the composition ofthe mixture to the quantity of active ingredient per unit weight ofwheat seed is observed.

    ______________________________________                                        Percent by weight                                                                             Percent by weight                                             of active antago-                                                                             of active antago-                                             nistic agent to nistic agent to                                               inert carrier   wheat seed after                                              (% composition) treatment (% on seed)                                         ______________________________________                                        1.25            0.125                                                         2.5             0.25                                                          5               0.5                                                           10              1.0                                                           ______________________________________                                    

In a similar fashion, the active safening agent is sometimes dissolvedor dispersed in one or more organic liquids. The solution or dispersionis mixed with the seed in a proportion to give the appropriate amount ofactive agent on the seed, as measured by weight, after the carrierliquid has been evaporated off.

The results of applying antagonistic agents as a seed treatment to wheatseed at various percentages by weight and applying triallate herbicideas a pre-emergent herbicide at various application rates is shown inTable II(A). Good control of weed species is observed.

                                      TABLE II (A)                                __________________________________________________________________________                                     Weight %  Percent                                   Amount of triallate       On Seed Of                                                                              Inhibition                                                                          Safening                     Example No.                                                                          Herbicide (kg./ha.)                                                                     Antagonistic Agent                                                                            Antagonistic Agent                                                                      Of Wheat                                                                            Effect                       __________________________________________________________________________                                                     (%)                          170    0.035     Methyl-N-ethyldithio-                                                                         0.0156    0     20                                            carbanilate                                                         0.035     Methyl-N-ethyldithio-                                                                         0.0312    0     20                                            carbanilate                                                         0.035     Methyl-N-ethyldithio-                                                                         0.0625    0     20                                            carbanilate                                                         0.035     Methyl-N-ethyldithio-                                                                         0.125     0     20                                            carbanilate                                                         0.035     Methyl-N-ethyldithio-                                                                         0.25      0     20                                            carbanilate                                                         0.07      Methyl-N-ethyldithio-                                                                         0.0156    50    0                                             carbanilate                                                         0.07      Methyl-N-ethyldithio-                                                                         0.0312    40    10                                            carbanilate                                                         0.07      Methyl-N-ethyldithio-                                                                         0.0625    15    35                                            carbanilate                                                         0.07      Methyl-N-ethyldithio-                                                                         0.125     10    40                                            carbanilate                                                         0.07      Methyl-N-ethyldithio-                                                                         0.25      5     45                                            carbanilate                                                         0.14      Methyl-N-ethyldithio-                                                                         0.0156    70    10                                            carbanilate                                                         0.14      Methyl-N-ethyldithio-                                                                         0.0312    70    10                                            carbanilate                                                         0.14      Methyl-N-ethyldithio-                                                                         0.0625    45    35                                            carbanilate                                                         0.14      Methyl-N-ethyldithio-                                                                         0.125     10    70                                            carbanilate                                                         0.14      Methyl-N-ethyldithio-                                                                         0.25      0     80                                            carbanilate                                                         0.28      Methyl-N-ethyldithio-                                                                         0.0156    85    10                                            carbanilate                                                         0.28      Methyl-N-ethyldithio-                                                                         0.0312    90    5                                             carbanilate                                                         0.28      Methyl-N-ethyldithio-                                                                         0.0625    85    10                                            carbanilate                                                         0.28      Methyl-N-ethyldithio-                                                                         0.125     50    45                                            carbanilate                                                         0.28      Methyl-N-ethyldithio-                                                                         0.25      10    85                                            carbanilate                                                         0.56      Methyl-N-ethyldithio-                                                                         0.0156    99    1                                             carbanilate                                                         0.56      Methyl-N-ethyldithio-                                                                         0.0312    90    10                                            carbanilate                                                         0.56      Methyl-N-ethyldithio-                                                                         0.0625    90    10                                            carbanilate                                                         0.56      Methyl-N-ethyldithio-                                                                         0.125     80    20                                            carbanilate                                                         0.56      Methyl-N-ethyldithio-                                                                         0.25      60    40                                            carbanilate                                                         1.12      Methyl-N-ethyldithio-                                                                         0.0156    100   0                                             carbanilate                                                         1.12      Methyl-N-ethyldithio-                                                                         0.0312    95    5                                             carbanilate                                                         1.12      Methyl-N-ethyldithio-                                                                         0.0625    95    5                                             carbanilate                                                         1.12      Methyl-N-ethyldithio-                                                                         0.125     95    5                                             carbanilate                                                         1.12      Methyl-N-ethyldithio-                                                                         0.25      85    15                                            carbanilate                                                  171    0.28      Ethyloctahydro-1H-azonine-                                                                    0.125     50    10                                            thionocarboxylate                                                   0.28      Ethyloctahydro-1H-azonine-                                                                    0.25      40    20                                            thionocarboxylate                                                   0.56      Ethyloctahydro-1H-azonine-                                                                    0.125     80    10                                            thionocarboxylate                                                   0.56      Ethyloctahydro-1H-azonine-                                                                    0.25      50    40                                            thionocarboxylate                                            172    0.14      Benzylisobutyldithiocarbamate                                                                 0.50      40    20                                  0.28      Benzylisobutyldithiocarbamate                                                                 0.50      35    40                                  0.56      Benzylisobutyldithiocarbamate                                                                 0.50      60    25                                  1.12      Benzylisobutyldithiocarbamate                                                                 0.50      65    33                           173    0.28      Methyl-N-methyldithio-                                                                        0.125     20    55                                            carbanilate                                                         0.28      Methyl-N-methyldithio                                                                         0.5       0     75                                            carbanilate                                                         0.56      Methyl-N-methyldithio-                                                                        0.125     55    40                                            carbanilate                                                         0.56      Methyl-N-methyldithio-                                                                        0.5       5     90                                            carbanilate                                                         1.12      Methyl-N-methyldithio-                                                                        0.125     80    10                                            carbanilate                                                         1.12      Methyl-N-methyldithio                                                                         0.5       5     90                                            carbanilate                                                  174    0.14      Methyl-N-methyldithio-                                                                        0.063     13    20                                            carbanilate                                                         0.14      Methyl-N-methyldithio-                                                                        0.125     18    15                                            carbanilate                                                         0.14      Methyl-N-methyldithio-                                                                        0.25      10    23                                            carbanilate                                                         0.14      Methyl-N-methyldithio-                                                                        0.5       15    18                                            carbanilate                                                         0.14      Methyl-N-methyldithio-                                                                        1.0       5     28                                            carbanilate                                                         0.28      Methyl-N-methyldithio-                                                                        0.063     45    30                                            carbanilate                                                         0.28      Methyl-N-methyldithio-                                                                        0.125     15    60                                            carbanilate                                                         0.28      Methyl-N-methyldithio-                                                                        0.25      10    65                                            carbanilate                                                         0.28      Methyl-N-methyldithio-                                                                        0.5       10    65                                            carbanilate                                                         0.28      Methyl-N-methyldithio-                                                                        1.0       10    65                                            carbanilate                                                         0.56      Methyl-N-methyldithio-                                                                        0.125     68    17                                            carbanilate                                                         0.56      Methyl-N-methyldithio-                                                                        0.25      45    40                                            carbanilate                                                         0.56      Methyl-N-methyldithio-                                                                        0.5       13    72                                            carbanilate                                                         0.56      Methyl-N-methyldithio-                                                                        1.0       15    70                                            carbanilate                                                         1.12      Methyl-N-methyldithio-                                                                        0.125     88    11                                            carbanilate                                                         1.12      Methyl-N-methyldithio-                                                                        0.25      73    26                                            carbanilate                                                         1.12      Methyl-N-methyldithio-                                                                        0.5       43    56                                            carbanilate                                                         1.12      Methyl-N-methyldithio-                                                                        1.0       13    86                                            carbanilate                                                         2.24      Methyl-N-methyldithio-                                                                        0.125     92    7                                             carbanilate                                                         2.24      Methyl-N-methyldithio-                                                                        0.25      80    19                                            carbanilate                                                         2.24      Methyl-N-methyldithio-                                                                        0.5       48    51                                            carbanilate                                                         2.24      Methyl-N-methyldithio-                                                                        1.0       20    79                                            carbanilate                                                  175    0.14      Tert. butylthiolcarbanilate                                                                   0.031     10    10                                  0.14      Tert. butylthiolcarbanilate                                                                   0.125     0     20                                  0.14      Tert. butylthiolcarbanilate                                                                   0.50      0     20                                  0.28      Tert. butylthiolcarbanilate                                                                   0.031     0     40                                  0.28      Tert. butylthiolcarbanilate                                                                   0.125     0     40                                  0.28      Tert. butylthiolcarbanilate                                                                   0.5       0     40                                  0.56      Tert. butylthiolcarbanilate                                                                   0.031     50    45                                  0.56      Tert. butylthiolcarbanilate                                                                   0.125     50    45                                  0.56      Tert. butylthiolcarbanilate                                                                   0.5       45    50                                  1.12      Tert. butylthiolcarbanilate                                                                   0.125     80    15                                  1.12      Tert. butylthiolcarbanilate                                                                   0.5       70    25                                  2.24      Tert. butylthiolcarbanilate                                                                   0.125     90    5                                   2.24      Tert. butylthiolcarbanilate                                                                   0.5       70    25                           176    0.28      Allyl-N-ethylthiono-                                                                          0.031     10    40                                            carbanilate                                                         0.28      Allyl-N-ethylthiono-                                                                          0.125     10    40                                            carbanilate                                                         0.28      Allyl-N-ethylthiono-                                                                          0.5       25    25                                            carbanilate                                                         0.56      Allyl-N-ethylthiono-                                                                          0.031     70    10                                            carbanilate                                                         0.56      Allyl-N-ethylthiono-                                                                          0.125     35    45                                            carbanilate                                                         0.56      Allyl-N-ethylthiono-                                                                          0.5       30    50                                            carbanilate                                                         1.12      Ally-N-ethylthiono-                                                                           0.031     85    15                                            carbanilate                                                         1.12      Allyl-N-ethylthiono-                                                                          0.125     75    25                                            carbanilate                                                         1.12      Allyl-N-ethylthiono-                                                                          0.5       25    75                                            carbanilate                                                         2.24      Allyl-N-ethylthiono-                                                                          0.125     7     30                                            carbanilate                                                         2.24      Allyl-N-ethylthiono-                                                                          0.5       90    10                                            carbanilate                                                  177    0.14      Methyl-N-isopropylthiono-                                                                     0.031     20    20                                            carbanilate                                                         0.14      Methyl-N-isopropylthiono-                                                                     0.125     15    25                                            carbanilate                                                         0.14      Methyl-N-isopropylthiono-                                                                     0.5       20    20                                            carbanilate                                                  178    0.28      Methyl-N-butylthiol-                                                                          0.031     30    40                                            carbanilate                                                         0.28      Methyl-N-butylthiol-                                                                          0.125     25    45                                            carbanilate                                                         0.28      Methyl-N-butylthiol-                                                                          0.50      40    30                                            carbanilate                                                         0.56      Methyl-N-butylthiol-                                                                          0.031     85    10                                            carbanilate                                                         0.56      Methyl-N-butylthiol-                                                                          0.125     35    60                                            carbanilate                                                         0.56      Methyl-N-butylthiol-                                                                          0.5       35    60                                            carbanilate                                                  179    0.14      2,3,3-trichloroallyl-N-(alpha-                                                                0.031     0     20                                            methylbenzyl)dithiocarbamate                                        0.14      2,3,3-trichloroallyl-N-(alpha-                                                                0.125     0     20                                            methylbenzyl)dithiocarbamate                                        0.14      2,3,3-trichloroallyl-N-(alpha-                                                                0.5       15    5                                             methylbenzyl)dithiocarbamate                                        0.28      2,3,3-trichloroallyl-N-(alpha-                                                                0.031     0     50                                            methylbenzyl)dithiocarbamate                                        0.28      2,3,3-trichloroallyl-N-(alpha-                                                                0.125     0     50                                            methylbenzyl)dithiocarbamate                                        0.28      2,3,3-trichloroallyl-N-(alpha-                                                                0.5       20    30                                            methylbenzyl)dithiocarbamate                                        0.56      2,3,3-trichloroallyl-N-(alpha-                                                                0.031     5     70                                            methylbenzyl)dithiocarbamate                                        0.56      2,3,3-trichloroallyl-N-(alpha-                                                                0.125     0     75                                            methylbenzyl)dithiocarbamate                                        0.56      2,3,3-trichloroallyl-N-(alpha-                                                                0.5       20    55                                            methylbenzyl)dithiocarbamate                                        1.12      2,3,3-trichloroallyl-N-(alpha-                                                                0.031     35    65                                            methylbenzyl)dithiocarbamate                                        1.12      2,3,3-trichloroallyl-N-(alpha-                                                                0.125     30    70                                            methylbenzyl)dithiocarbonate                                        1.12      2,3,3-trichloroallyl-N-(alpha-                                                                0.5       15    85                                            methylbenzyl)dithiocarbamate                                        2.24      2,3,3-trichloroallyl-N-(alpha-                                                                0.125     60    40                                            methylbenzyl)dithiocarbamate                                        2.24      2,3,3-trichloroallyl-N-(alpha-                                                                0.5       20    80                                            methylbenzyl)dithiocarbamate                                 180    0.14      Methyl-N-butyldithio-                                                                         0.031     0     35                                            carbanilate                                                         0.14      Methyl-N-butyldithio-                                                                         0.125     10    25                                            carbanilate                                                         0.14      Methyl-N-butyldithio-                                                                         0.500     10    25                                            carbanilate                                                         0.28      Methyl-N-butyldithio-                                                                         0.031     15    60                                            carbanilate                                                         0.28      Methyl-N-butyldithio-                                                                         0.125     15    60                                            carbanilate                                                         0.28      Methyl-N-butyldithio-                                                                         0.500     15    60                                            carbanilate                                                         0.56      Methyl-N-butyldithio-                                                                         0.031     55    43                                            carbanilate                                                         0.56      Methyl-N-butyldithio-                                                                         0.125     50    48                                            carbanilate                                                         0.56      Methyl-N-butyldithio-                                                                         0.500     35    63                                            carbanilate                                                  __________________________________________________________________________

EXAMPLES 181 to 185

These examples illustrate the application of the antagonistic agents ofthis invention as seed treatments to protect desired crops fromherbicidal injury by thiolcarbamate herbicides other than triallate. Inthese examples the herbicide is applied to the soil as in Examples 1 to169. However, the antagonistic agent is applied to crop seed as inExamples 170 to 180. The results are tabulated in Table II (B) whichshow the safening effect of the antagonistic agents of this invention.

In order to counteract injury by the thiolcarbamate herbicide, the cropseed need to treated with only a small amount of the antagonistic agent.For example, application rates of about 1100 g. to as low as about 1.5g. of active agent per bushel of seed may be used. The presentlypreferred application rate is in the range of about 3 g. to 550 g. ofagent per bushel. The seed is treated with an antagonistic agent by useof conventional seed treating apparatus well known to the art. The seedis thoroughly mixed with the antagonistic agent in the seed treatingapparatus, thereby giving a seed which is coated with the agent.

Since only a very small amount of active antagonistic agent is requiredfor the seed treatment, the compound preferably is formulated as awettable powder or an emulsifiable concentrate which can be diluted withwater by the seed treater for use in the seed treating apparatus. Ofcourse, under certain conditions, it may be desirable to dissolve theantagonistic agent in an organic solvent for use as a seed treatment orthe pure compound alone may be used under properly controlledconditions.

There are thus also provided by this invention novel seed treatingcompositions containing one or more of the described active antagonisticagents intimately dispersed in an inert carrier or diluent for theintended use. Such carriers may be either solids, such as talc, clay,diatomaceous earth, sawdust, calcium carbonate, and the like or liquidssuch as water, kerosene, acetone, benzene, toluene, xylene, and the likein which the active agent may be either dissolved or dispersed.Emulsifying agents are advisably used to achieve a suitable emulsion iftwo immiscible liquids are used as a carrier. Wetting agents may also beused to aid in dispersing the active antagonistic agent in liquids usedas a carrier in which the agent is not completely soluble. Emulsifyingagents and wetting agents, also known as "surface active agents", aresold under numerous tradenames and may be either pure compounds,mixtures of compounds of the same general groups, or they may bemixtures of compounds of different classes. Typical satisfactory surfaceactive agents which may be used are alkali metal higheralkylarylsulfonates such as sodium dodecylbenzenesulfonate and thesodium salts of alkylnaphthalenesulfonic acids, fatty alcohol sulfatessuch as the sodium salts of monoesters of sulfuric acid with n-aliphaticalcohols containing 8-18 carbon atoms, long chain quaternary ammoniumcompounds, sodium salts of petroleum-derived alkylsulfonic acids,polyethylene sorbitan monooleate, alkylaryl polyester alcohols,water-soluble lignin sulfonate salts, alkali casein compositions, longchain alcohols usually containing 10 to 18 carbon atoms, andcondensation products of ethylene oxide with fatty acids, alkylphenolsand mercaptans.

                                      TABLE II (B)                                __________________________________________________________________________           Amount         Weight %              Percent                                  Herbicide      On Seed Of            Inhibition                                                                          Safening                    Example No.                                                                          (kg./ha.)                                                                           Herbicide                                                                              Antagonistic Agent                                                                      Safening Agent                                                                            Of Wheat                                                                            Effect(%)                   __________________________________________________________________________    181    0.28  diallate 0.031     tertiary butylthiol-                                                                      85    15                                                          carbanilate                                          0.28  diallate 0.125     tertiary butylthiol-                                                                      80    20                                                          carbanilate                                          0.28  diallate 0.5       tertiary butylthiol-                                                                      60    40                                                          carbanilate                                   182    0.28  diallate 0.031     2,3,3-trichloroallyl-                                                                     80    18                                                          N-alpha-methylbenzyl-                                                         dithiocarbamate                                      0.28  diallate 0.125     2,3,3-trichloroallyl-                                                                     50    48                                                          N-alpha-methylbenzyl-                                                         dithiocarbamate                                      0.28  diallate 0.5       2,3,3-trichloroallyl-                                                                     20    78                                                          N-alpha-methylbenzyl-                                                         dithiocarbamate                               183    0.28  diallate 0.031     methyl-N-ethyldithio-                                                                     50    40                                                          carbanilate                                          0.28  diallate 0.125     methyl-N-ethyldithio-                                                                     25    65                                                          carbanilate                                          0.28  diallate 0.5       methyl-N-ethyldithio-                                                                     20    70                                                          carbanilate                                   184    0.28  diallate 0.031     methyl-N-methyldithio-                                                                    70    25                                                          carbanilate                                          0.28  diallate 0.125     methyl-N-methyldithio-                                                                    40    55                                                          carbanilate                                          0.28  diallate 0.5       methyl-N-methyldithio-                                                                    75    20                                                          carbanilate                                   185    0.28  S-propyl-N-butyl-                                                                      0.031     methyl-N-methyldithio-                                                                    70    15                                       N-ethylthiol-      carbanilate                                                carbamate                                                               0.28  S-propyl-N-butyl-                                                                      0.125     methyl-N-methyldithio-                                                                    40    45                                       N-ethylthiol-      carbanilate                                                carbamate                                                               0.28  S-propyl-N-butyl-                                                                      0.5       methyl-N-methyldithio-                                                                    40    45                                       N-ethylthiol-      carbanilate                                                carbamate                                                        __________________________________________________________________________

EXAMPLES 186 to 205

The procedure of Examples 1 to 169 is followed except that, instead ofapplying the antagonistic agent as a sequential spray before applicationof the thiolcarbamate herbicide, the antagonistic agent andthiolcarbamate herbicide are applied to the soil together as a mixtureto give the amounts for each shown for each example in Table III. Goodcontrol of weeds is noted in each example.

                                      TABLE III                                   __________________________________________________________________________         Amount         Amount Antag-            Percent                                                                            Safening                    Example                                                                            Herbicide      onistic Agent            Inhibi-                                                                            Effect                      No.  (kg./ha.)                                                                           Herbicide                                                                              (kg./ha.)                                                                             Antagonistic Agent                                                                        Crop tion (%)                         __________________________________________________________________________    186  0.28  diallate 8.96    allyl-N-methyldithio-                                                                     Wheat                                                                              70   20                                                      carbanilate                                            0.28  diallate 8.96    allyl-N-methyldithio-                                                                     Sorghum                                                                            50   47                                                      carbanilate                                            0.28  diallate 8.96    methyl-N-ethyldithio-                                                                     Wheat                                                                              20   70                                                      carbanilate                                            0.28  diallate 8.96    methyl-N-ethyldithio-                                                                     Sorghum                                                                            65   32                                                      carbanilate                                       187  0.28  S-ethyl-N,N-                                                                           8.96    allyl-N-methyldithio-                                                                     Wheat                                                                              60   13                                     dipropylthiol-   carbanilate                                                  carbamate                                                               0.28  S-ethyl-N,N-                                                                           8.96    allyl-N-methyldithio-                                                                     Sorghum                                                                            70   22                                     dipropylthiol-   carbanilate                                                  carbamate                                                          188  0.28  S-ethyl-N-ethyl-                                                                       8.96    allyl-N-methyldithio-                                                                     Sorghum                                                                            60   15                                     N-cyclohexane-   carbanilate                                                  thiolcarbamate                                                     189  0.28  triallate                                                                              8.96    allyl-N-methyldithio-                                                                     Wheat                                                                              55   42                                                      carbanilate                                            0.28  triallate                                                                              8.96    alyl-N-methyldithio-                                                                      Sorghum                                                                            15   84                                                      carbanilate                                       190  0.28  triallate                                                                              8.96    methyl-N-ethyldithio-                                                                     Wheat                                                                              25   72                                                      carbanilate                                            0.28  triallate                                                                              8.96    methyl-N-ethyldithio-                                                                     Sorghum                                                                            55   44                                                      carbanilate                                            8.96  triallate                                                                              8.96    methyl-N-ethyldithio-                                                                     Sorghum                                                                            75   24                                                      carbanilate                                       191  0.28  S-propyl-N-butyl-                                                                      8.96    allyl-N-methyldithio-                                                                     Sorghum                                                                            60   38                                     N-ethylthio-     carbanilate                                                  carbamate                                                          192  0.28  S-propyl-N-butyl-                                                                      8.96    methyl-N-ethyldithio-                                                                     Sorghum                                                                            70   28                                     N-ethylthio-     carbanilate                                                  carbamate                                                          193  0.28  S-ethyl-N,N-                                                                           8.96    allyl-N-methyldithio-                                                                     Sorghum                                                                            65   23                                     diisobutylthiol- carbanilate                                                  carbamate                                                          194  0.28  S-ethyl-N,N-                                                                           8.96    methyl-N-ethyldithio-                                                                     Sorghum                                                                            75   13                                     diisobutylthiol- carbanilate                                                  carbamate                                                          195  0.28  S-propyl-N,N-                                                                          8.96    allyl-N-methyldithio-                                                                     Sorghum                                                                            75   15                                     dipropylthiol-   carbanilate                                                  carbamate                                                          196  8.96  diallate 8.96    allyl-N-methyldithio-                                                                     Corn  5   30                                                      carbanilate                                       197  8.96  S-ethyl-N,N-di-                                                                        8.96    allyl-N-methyldithio-                                                                     Corn 30   45                                     propylthiolcar-  carbanilate                                                  bamate                                                             198  8.96  S-ethyl-N,N-di-                                                                        8.96    methyl-N-ethyldithio-                                                                     Corn 40   35                                     propylthiolcar-  carbanilate                                                  bamate                                                             199  8.96  S-ethyl-N-ethyl-                                                                       8.96    methyl-N-ethyldithio-                                                                     Corn 65   23                                     thiolcyclohexane-                                                                              carbanilate                                                  carbamate                                                          200  8.96  triallate                                                                              8.96    allyl-N-methyldithio-                                                                     Corn 10   25                                                      carbanilate                                       201  8.96  triallate                                                                              8.96    methyl-N-ethyldithio-                                                                     Corn 10   25                                                      carbanilate                                       202  8.96  S-propyl-N-butyl-                                                                      8.96    allyl-N-methyldithio-                                                                     Corn 70   10                                     N-ethylthiolcar- carbanilate                                                  bamate                                                             203  8.96  S-propyl-N-butyl-                                                                      8.96    methyl-N-ethyldithio-                                                                     Corn 60   20                                     N-ethylthiolcar- carbanilate                                                  bamate                                                             204  8.96  S-propyl-N,N-di-                                                                       8.96    allyl-N-methyldithio-                                                                     Corn 55   28                                     propylthiolcar-  carbanilate                                                  bamate                                                             205  8.96  S-propyl-N,N-di-                                                                       8.96    methyl-N-ethyldithio-                                                                     Corn 70   13                                     propylthiolcar-  carbanilate                                                  bamate                                                             __________________________________________________________________________

EXAMPLE 206

This example illustrates the safening effect of a representativeantagonistic agent of this invention, methyl-N-ethyldithiocarbanilate,as a wheat seed treatment with a representative thiolcarbamateherbicide, triallate, applied as a pre-emergent herbicide after thetreated wheat seed is planted in a number of different soil types. Theprocedure of Examples 170 to 185 is employed and the soil in which thetreated wheat seed is planted is as designated in Table IV. Good weedcontrol and safening of the herbicide is noted for each soil type.

                  TABLE IV                                                        ______________________________________                                                            Amount of                                                                     methyl-N-ethyl-                                                                            Inhibi-                                      Amount              dithiocarbanilate                                                                          tion  Safen-                                 of                  antagonistic of    ing                                    triallate           agent applied                                                                              Wheat Effect                                 herbicide           as a seed treat-                                                                           (per- (per-                                  (kg/ha)                                                                              Soil Type    ment (weight %)                                                                            cent) cent)                                  ______________________________________                                        2.24   Ray silt loam                                                                              0.25         75    18                                     2.24   Florida sand 0.25         28    45                                     2.24   Norfolk sandy                                                                              0.25         25    40                                             loam                                                                  2.24   Drummer silty                                                                              0.25         55    38                                             clay loam                                                             2.24   Sarpy silty  0.25         65    23                                             clay loam                                                             2.24   Wabash silty 0.25         60    30                                             clay loam                                                             ______________________________________                                    

EXAMPLE 207

This example illustrates the use of a representative antagonistic agent,methyl-N-ethyldithiocarbanilate, as a wheat seed treatment formulatedwith a variety of carriers to safen the plant inhibition effect on wheatof a representative thiolcarbamate herbicide. The procedure of Examples170 to 185 is followed except that the carriers designated in Table Vare employed with the results shown. In each instance good control ofweeds is observed.

                                      TABLE V                                     __________________________________________________________________________    Amount of               Amount of methyl-N-ethyl-                             triallate               dithiocarbanilate antago-                                                                   Inhibition                              herbicide               nistic agent applied as a                                                                   of Wheat                                                                            Safening Effect                   (kg/ha)                                                                             Carrier           seed treatment (weight %)                                                                   (percent)                                                                           (percent)                         __________________________________________________________________________    0.56  acetone           0.25          15    55                                0.56  methanol          0.25          15    55                                0.56  ethanol           0.25          20    50                                0.56  isopropanol       0.25          20    50                                0.56  20 percent by weight of                                                                         0.25          30    40                                      dimethylsulfoxide in acetone                                            0.56  dichloromethane   0.25          13    57                                0.56  ethyl acetate     0.25          23    47                                0.56  toluene           0.25          15    55                                0.56  powder formulation                                                                              0.25          18    52                                       30 percent by weight                                                           dipropylene glycol                                                           20 percent by weight                                                           calcium silicate                                                      0.56  95 percent by weight kaolinite                                                                  0.25          13    57                                      1.5 percent by weight dipropylene                                              glycol                                                                       1 percent by weight calcium silicate                                    __________________________________________________________________________

EXAMPLES 208 TO 213

These examples illustrate the application of representative antagonisticagents of this invention as seed treatments to protect corn (maize) fromherbicidal injury by thiolcarbamate herbicides. In these examples theherbicide is applied to the soil as in Examples 1 to 169. However, theantagonistic agent is applied to corn seed as in Examples 170 to 186.The results are tabulated in Table VI which show the safening effect ofthe antagonistic agents of this invention as seed treatment on corn.Good control of weeds is noted for each example.

                                      TABLE VI                                    __________________________________________________________________________                     Weight %          Percent                                         Amount      On Corn           Inhibi-                                                                            Safening                              Example                                                                            Herbicide   Seed Of Antag-    tion Effect                                No.  (kg./ha.)                                                                           Herbicide                                                                           onistic Agent                                                                         Antagonistic Agent                                                                      Of Corn                                                                            (%)                                   __________________________________________________________________________    208  8.96  diallate                                                                            0.031   Methyl-N-methyl-                                                                        60    5                                                             dithiocarbanilate                                         8.96  diallate                                                                            0.125   Methyl-N-methyl-                                                                        25   35                                                             dithiocarbanilate                                         8.96  diallate                                                                            0.5     Methyl-N-methyl-                                                                        10   50                                                             dithiocarbanilate                                    209  8.96  EPTC  0.5     Methyl-N-methyl-                                                                        40   25                                                             dithiocarbanilate                                    210  8.96  vernolate                                                                           0.031   Methyl-N-methyl-                                                                        85    5                                                             dithiocarbanilate                                         8.96  vernolate                                                                           0.125   Methyl-N-methyl-                                                                        40   50                                                             dithiocarbanilate                                         8.96  vernolate                                                                           0.5     Methyl-N-methyl-                                                                        40   50                                                             dithiocarbanilate                                    211  8.96  pebulate                                                                            0.5     Methyl-N-methyl-                                                                        45   35                                                             dithiocarbanilate                                    212  8.96  diallate                                                                            0.125   Methyl-N-ethyl-                                                                         30   10                                                             dithiocarbanilate                                         8.96  diallate                                                                            0.5     Methyl-N-ethyl-                                                                         10   30                                                             dithiocarbanilate                                    213  8.96  butylate                                                                            0.031   Methyl-N-ethyl-                                                                         0    25                                                             dithiocarbanilate                                         8.96  butylate                                                                            0.125   Methyl-N-ethyl-                                                                         0    25                                                             dithiocarbanilate                                         8.96  butylate                                                                            0.5     Methyl-N-ethyl-                                                                         0    25                                                             dithiocarbanilate                                    __________________________________________________________________________

While this invention has been described with respect to certainembodiments, it is to be understood that it is not so limited and thatvariations and modifications thereof obvious to those skilled in the artto which this invention appertains can be made without departing fromthe spirit or scope thereof.

What is claimed is:
 1. A method for reducing injury to wheat, sorghumand corn by thiolcarbamate herbicides selected from the group consistingof S-2-dichloroallyl N,N-diisopropylthiocarbamate andS-2,3,3-trichloroallyl N,N-diisopropylthiolcarbamate which comprisesapplying to the soil, crop or crop seed an effective safening amount ofa compound of the formula ##STR9## wherein R is lower alkyl, R' ishydrogen and R² is phenyl.
 2. A method of claim 1 wherein the compoundis incorporated into the soil.
 3. Method of claim 1 wherein R istert-butyl.
 4. A safened herbicide composition comprising athiolcarbamate herbicide selected from the group consisting ofS-2,3-dichloroallyl N,N-diisopropylthiolcarbamate andS-2,3,3-trichloroallyl N,N-diisopropylthiolcarbamate and an effectivesafening amount of a compound of the formula ##STR10## wherein R islower alkyl, R¹ is hydrogen and R² is phenyl.
 5. Composition of claim 4wherein R is tert-butyl.